Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
  • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
  • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
  • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
  • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
  • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
  • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
  • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
  • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
  • C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
  • C08G18/725—Combination of polyisocyanates of C08G18/78 with other polyisocyanates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
  • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
  • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2120/00—Compositions for reaction injection moulding processes

Definitions

• the invention relates to a new process for the preparation of light-resistant, optionally foamed, elastic polyurethane moldings by reaction in closed forms of organic polyisocyanates with compounds having at least two groups which are reactive toward isocyanate groups, with the use of catalysts and optionally the customary auxiliaries and additives, where as Polyisocyanates certain mixtures of selected polyisocyanates with aliphatic or cycloaliphatic bound isocyanate groups are used.
• DE-OS 3 008 811 recommends using compounds containing primary or secondary amino groups in combination with an organic bismuth compound to catalyze the polyurethane formation reaction.
• DE-OS 2 447 067 and DE-OS 2 710 901 recommend special combinations of certain amines, amidines or guanidines with alkaline earth metal salts or combinations of compounds with primary or secondary amino groups with lead compounds.
• DE-OS 2 825 569 recommends combinations of alkali compounds and / or of hexahydrotriazine derivatives with organic tin, zinc and / or iron (II) compounds.
• DE-OS 2 832 253 finally recommends alkali and alkaline earth metal hydroxides in combination with organic tin, lead and iron compounds.
• the polyisocyanate component a) to be used in the process according to the invention is a mixture a1) or a2) of the type already mentioned above.
• a mixture a1) is particularly preferably used as the polyisocyanate component a), which comprises 10 to 70, in particular 35 to 65 Wt .-% consists of IPDI.
• Component (ii) preferably has an NCO content of 18 to 23% by weight.
• the preparation of the individual component (ii) by partial trimerization of 1,6-diisocyanatohexane can be carried out, for example, according to US Pat. No. 4,324,879 or EP Pat. No. 10,589, and the preparation of the component (iii) by mixed trimer
• the HDI and IPDI can be set, for example, in accordance with DE-OS 3,033,860.
• the polyisocyanate component a2) preferably consists of 35 to 65% by weight of free IPDI.
• mixtures HDI and IPDI are used which have up to 4 parts by weight of IPDI per part by weight of HDI.
• the weight ratio HDI: IPDI is preferably 4: 1 to 1: 4.
• Component (iii) preferably has an NCO content of 17 to 22% by weight.
• Component b) is generally a mixture of b1) higher molecular weight polyether polyols with b2) low molecular weight chain extenders or crosslinking agents.
• Component b1) is a polyether polyol with a molecular weight in the range from 500 to 10,000, preferably 2,000 to 8,000, with two or three terminal hydroxyl groups or a mixture of polyether polyols in the stated molecular weight with a (mean) hydroxyl functionality of 2 to 3.
• the polyether polyols are in obtained in a manner known per se by alkoxylation of suitable starter molecules such as, for example, glycerol, trimethylolpropane, water, propylene glycol or ethylene glycol. If mixtures of di- and trifunctional polyether polyols of the stated hydroxyl functionality are used, the mixtures can be prepared by alkoxylation of a corresponding starter mixture or by mixing separately prepared polyether polyols.
• Alkoxylating agents are propylene oxide and ethylene oxide, which can optionally also be used in a mixture.
• the polyether chains of the polyether polyols preferably consist of at least 50% by weight of propylene oxide units, but with the proviso that in the alkoxylation reaction, pure ethylene oxide in the end in an amount of at least 5% by weight, preferably at least 10% by weight, based on the total weight of all alkylene oxides used.
• the proportion of component b1) in such ethylene oxide-typed polyether polyols is preferably at least 80% by weight, based on the total weight of component b1).
• Particularly preferred polyether polyols are those which have been obtained by propoxylation of the starter molecules mentioned by way of example and subsequent ethoxylation of the propoxylation product, the weight ratio propylene oxide: ethylene oxide being 50:50 to 95: 5, preferably 70:30 to 90:10.
• the molecular weight of the polyether polyols can be calculated from the hydroxyl functionality and the hydroxyl group content.
• Component b2) is, in the sense of the isocyanate addition reaction, di- and / or trifunctional compounds with a molecular weight below 500.
• Component b2) preferably contains di- and / or trialkanolamines, preferably exclusively secondary or tertiary amino groups such as diethanolamine, triethanolamine, N-methyl-diethanolamine, or, less preferably, corresponding compounds with secondary hydroxyl groups such as dipropanolamine, tripropanolamine or N-methyl-dipropanolamine.
• Diethanolamine is very particularly preferably used. In principle, mixtures of such di- and trialkanolamines can also be used.
• nitrogen-free alkane diols and / or triols can also be used as chain extenders or crosslinking agents. Accordingly, mixtures of the di- and / or trialkanolamines mentioned by way of example with such nitrogen-free polyols are also highly suitable as component b2). In such mixtures which are highly suitable as component b2), the proportion of nitrogen-free polyols, based on the total weight of component b2), is generally at most 70% by weight.
• nitrogen-free compounds examples include diols such as ethylene glycol, diethylene glycol, triethylene glycol, Tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 1,2-, 1,4- or 2,3-dihydroxybutane, 1,6-dihydroxyhexane, technical octane diol isomer mixtures or any mixtures of such diols and moreover triols such as glycerol, trimethylol propane or the alkoxylation, preferably propoxylation products of these triols insofar as their molecular weight is below 500.
• Component b2) is used in amounts such that 3 to 50, preferably 5 to 30 parts by weight of component b2) are present in the reaction mixture per 100 parts by weight of component b1).
• the catalysts c) are organic tin and / or lead compounds, in particular dialkyltin (IV) salts or lead (II) salts of carboxylic acid, the alkyl radicals linked to the tin atom having 1 to 4 carbon atoms and the indifferent hydrocarbon radicals of preferably aliphatic carboxylic acids preferably have 7 to 11 carbon atoms.
• Examples of such lead or tin catalysts are dimethyltin dilaurate, dimethyltin dioctoate, dibutyltin dilaurate, dimethyltin dioctoate or lead (II) octoate.
• the dimethyltin compounds mentioned by way of example, in particular dimethyltin dilaurate, are preferably used.
• Suitable amine catalysts are, for example, triethylene diamine or N, N-dimethylbenzylamine.
• the catalysts are used in an amount of 0.01 to 5 parts by weight, preferably 0.2 to 2 parts by weight, per 100 parts by weight of component b1).
• auxiliaries and additives d) which may be used are, for example d1) blowing agents such as water and / or volatile organic substances such as acetone, ethyl acetate, halogen-substituted alkanes such as methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane, chlorifluoromethane or dichlorodifluoromethane.
• a driving effect can also be achieved by adding compounds which decompose at temperatures above room temperature with the elimination of gases, for example nitrogen, for example azo compounds such as azodicarbonamide or azoisobutyronitrile.
• propellants as well as details on the use of propellants can be found in the Kunststoff-Handbuch, Volume VII, published by Vieweg and Höchtlen, Carl-Hanser-Verlag, Kunststoff 1966, e.g. on pages 108 and 109, 453 to 455 and 507 to 510 described.
• auxiliaries and additives that may be used are, for example d2) light stabilizers.
• these include, for example, piperidine derivatives such as 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-1,2,2,6,6-pentamethylpiperidine, bis- (2,2,6,6-tetramethyl-4- piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) suberate or bis (2,2,6,6-tetramethyl-4-piperidyl) dodecanedioate;
• Benzophenone derivatives such as 2,4-dihydroxy, 2-hydroxy-4-methoxy, 2-hydroxy-4-octoxy, 2-hydroxy-4-dodecyloxy or 2,2oxy-dihydroxy-4-dodecyloxy-benzophenone;
• Benzotriazole derivatives such as 2- (2 ⁇ -hydroxy-3 ⁇ , 5 ⁇ -di-tert-amylphenyl
• the aforementioned light stabilizers are used individually or in combinations. Mixtures of piperidine and benzotriazole derivatives are preferred.
• auxiliaries and additives that may be used are d3) surface-active additives (emulsifiers and foam stabilizers).
• suitable emulsifiers are the sodium salts of castor oil sulfonates or also of fatty acids or salts of fatty acids with amines such as oleic acid diethylamine or stearic acid diethanolamine.
• Alkali or ammonium salts of sulfonic acids such as dodecylbenzenesulfonic acids or also of fatty acids such as ricinoleic acid or of polymeric fatty acids can also be used as surface-active additives, as well as ethoxylated nonylphenol.
• Foam stabilizers in particular are polyether siloxanes, especially water-soluble representatives. These compounds are generally designed so that a copolymer of ethylene oxide and propylene oxide is linked to a polydimethylsiloxane radical. Such foam stabilizers are e.g. in U.S. Patents 2,834,748, 2,917,480, and 3,629,308. Of particular interest are polysiloxane-polyoxyalkylene copolymers, which are branched via allophanate groups, in accordance with DE Offenlegungsschrift 2,558,523.
• the aforementioned emulsifiers or stabilizers are preferably used individually, but also in any combination.
• auxiliaries and additives which may be used are cell regulators of the type known per se, such as paraffins or fatty alcohols, pigments or dyes, flame retardants of the type known per se, such as e.g. Trischloroethyl phosphate or ammonium phosphate and polyphosphate or fillers such as barium sulfate, diatomaceous earth, soot, sludge chalk or glass fibers with a reinforcing effect.
• the inner mold release agents known per se can also be used in the process according to the invention.
• components b1) and b2) are preferably mixed to give a "polyol component” b) which is then processed with the polyisocyanate component a) as a “one-shot system".
• the catalysts c) and any auxiliaries and additives d) which may be used are incorporated into the reaction partners mentioned.
• the organic blowing agents and the light stabilizers of the polyisocyanate component a) and the catalysts c) and any other auxiliaries and additives d) which may be used can be mixed into the polyol component.
• NCO index NCO / H active equivalent ratio x 100
• the reactive mixture is introduced into closed molds (for example steel or aluminum molds), the inner walls of which may have been coated with the usual external mold release agents.
• the amount of the reaction mixture introduced into the mold and also the amount of any blowing agent also used depends on the desired density of the molding. When the mold is completely filled, massive molded parts are formed which, depending on the type and amount of the fillers which may be used, have a density of approximately 1.0 to 1.4 g / cm3.
• microcellular density range about 0.8 to 1.0 g / cm3
• foamed total density about 0.1 to 0.8, preferably
• the temperature of the mixture to be introduced into the mold is generally 20 to 60 ° C., preferably 20 to 50 ° C.
• the temperature of the molds is kept at 40 to 90, preferably 55 to 65 ° C. when carrying out the process according to the invention.
• the moldings can generally be removed from the mold after a mold life of 3 to 10 minutes.
• the elastic molded parts according to the invention thus obtained have excellent mechanical properties and excellent light and in particular UV stability. They are suitable, for example, for the manufacture of upholstered parts such as armrests, seat pads in furniture and vehicle construction, elastic handles for tools and operating elements, elastic pads, bumper corners for furniture and bumpers or rubbing strips for vehicles.
• Stabilizer I Commercial polyether polysiloxane stabilizer ("Stabilizer DC 193" from DOW Corning).
• Stabilizer II bis (2,2,6,6-tetramethyl-4-piperidly) sebacate.
• Stabilizer III 2- (2 ⁇ -hydroxy-3 ⁇ , 5 ⁇ -di-t-amylphenyl) benzotriazole.
• Polyisocyanate II trimerized hexamethylene diisocyanate.
• Example IX The amount of the reaction mixture introduced into the molds was in each case measured so that molded articles with a density of 0.4 g / cm 3 resulted.
• the moldings were removed from the mold after a mold life of 5 to 10 minutes. This resulted in light-resistant, foamed, elastic molded articles which have a closed surface layer. Only in Example IX was no blowing agent added; the recipe used here is suitable, for example, for the production of solid molded parts.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Polyurethanes Or Polyureas (AREA)

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• 1988
  • 1988-01-05 EP EP88100030A patent/EP0275010B1/fr not_active Expired - Lifetime
  • 1988-01-05 DE DE8888100030T patent/DE3866247D1/de not_active Expired - Lifetime
  • 1988-01-11 CA CA000556214A patent/CA1300304C/fr not_active Expired - Lifetime
  • 1988-01-11 US US07/142,759 patent/US4772639A/en not_active Expired - Fee Related

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